7 D-We6 31 PLYMER ELECTROLYTE ASED ON POLY(ETHYLENE

ININE) AMO 1/1LITHIUM SALTS(U) NATIONAL BUREAU OF STANDARDSOAITHERSBURG ND POLYMERS DIV C K CHIANG ET AL.

UNLSIII 1OCT 65 TR-3 N66S14-B5-F-6S22 FI/G 7/4 IN

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1i. RIEPORT NUGRp oWTACCESSION X RECIPSENVS CATAL.OGINUNDER~

STechnical Report 3. / .

TL TP OF N9PONT PERIOO COVILRED

POLYMER ELECTROLYTE BASED ON POLY(ETHYLENE .cbpic* R rt 3.IMINE) AND LITHIUM SALTS s. PwOawr, o. REPO NUUEN

AUTNOR(*) S. CONTRACT ON GRANT NUSUR(). "

C. K. Chiang, G. T. Davis, C. A. Harding, and N00014-85-F022T T. Takahashi _

P'ERFORMING ORGANIZATION NAMIE IS. PROGRAM ILIlMENT. PROJECT. TASKAN -. ~ORS ARIA G WORK UNIT NUMURS

National Bureau of Standards-Polymers DivisiQn Task No. 14339i_Gaithersburg. MD 20899

•CONTROLLING OFFICE NAMC AND ADORES IS. REPORT OATE

Office of Naval Research October 1. 1985V. U91ROFPGo IArlington, VA 22217 14 UME F AE

MONITORING AUENCY NAMI AODRIIOt d4bm# h COWM*1d OffI00) IL SEiCURITY CLASS. (of1do.9410inm

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i:;: " OCT 1 i

ILS SUPPLIEMENTARY NOTUS

- Submitted to Solid State Ionics

II. KEY WORDS (C&autbn = mveee aid at amem m amo U 1 yfr Alobr "OaI

. Battery; conductivity; ionic conduction; lithium salts; poly(ethylene imine);polymeric electrolyt .

.-' L- -

.AMjTfASCT LfOmmio US0o. aId0 It .emeOm OW I~& b &F 10011

Iuon lithium salts in linear poly(ethylene imine) has be4n in-vestigated because of its possible role as a solid electrolyte in lithium

-batteries. Lithium salts included in the study are LiF, LiCI, LiBr, LII, LiSCN,. LiClO1 and LiBF1. When-cast from solution in a common solvent, a unifqrm mix-

ture ts obtained (except for the case of LiF). Interaction of the sald andpolymer can be characterized by observing a loss in crystallinity of the polymeand an increase in the glass transition temperature. At toncentration4 of salt

. below 10 mole percent, the polymer can slowly recrystallize at room tey4perature

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tat b4ghar concenti-ations, the mixtuire remains amorphous fo n..ndefinitep~rid o t~~~)D~co'nduct v ty at room temperature is about 1'O Sc u

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OFFICE OF NAVAL RESEARCH

Contract N00014-85-FO022

Task No. 14339

TECHNICAL REPORT NO. 3

POLYMER ELECTROLYTE BASED ON POLY(ETHYLENE IMINE)AND LITHIUM SALTS

by

C. K. Chiang, G. T. Davis, C. A. Harding and T. Takahashi

Prepared for Publication

in

Solid State Ionics

.National Bureau of StandardsCenter for Materials Science

Polymers DivisionGaithersburg, MD

October 1, 1985

,J.

Reproduction in whole or in part is permitted forany purpose of the United States Government.

This document has been approved for public releaseand sale; its distribution is unlimited.

85 10 17 01.1• .... *.,,.... .....-... ,. ..... , :, . -,%S 9,,.., ,- . . . -,., ,9..,., , . ... % . , ,,

POLYMERIC ELECTROLYTE BSED ON POLY(ETHYLENE IMINE) AND LITHIUM SALTS

C. K. Chiang. G. T. Davis and C. A. Harding

National Bureau of Standards, Gaithersburg, 10 20899 USA

and

T. TAKAHASHI

UM Industries, Tokyo, Japan

The dissolution of lithium salts in linear poly(ethylene lmne) has been investigated because ofits possible role as a solid electrolyte in lithium batteries. Lithiun salts included in thestudy are LiF, LIC1, Litr, Lit, LiSCI, LiCIO and LIBF. When cast from solution in a Comon sol-vent, a uniform mixture is obtained (except for the cale of LiF). Interaction of the salt andpolymer can be characterized by observing a loss in crystallinity of the polymer and an Increasein the glass transition temperature. At concentrations of salt below 10 mole percent, the polymercan slowly recrystallize at room temperature but at higher concentrations, the mixture remainsamorhous for an indefinite period of time. DC conductivity at rem temperature is aboutlxlO S/cm but increases to lx10" S/cm at 150 1C.

1. INTROUCTION usually observed for Na/0 in the PEO coa-4, Te dissolution of alkali metal salts in plex4 ,8 . Ionic conductivity of the PEI-salt, oxygen-containing polymers such as polyethy- mixtures in most cases is comparable to that

a, lene oxide)1"4, poly(propylene oxide)4"6 , and reported for PEO-salt mixtures. Results ob-

poly(ethylene succinato)7 is believed to in- tathed for a variety of lithitu salts in lin-

volve strong interaction between the cation ear poly(ethylene mine) will be presented in

and the unshared electron pairs of the oxygen. this report.

We have examined linear poly(othylene iline),

(-%CH2NK-)n as a host polymer for electro- 2. EXPERIMENTALlytes8 because of the unshared electron pair A. Preparation of polymer and complexes

on nitrogen. Many of the phomna observed The poly(ethylene amte) which is availableare analogous to those of poly(ethylen ox- commercially is highly branched, non-crystal-

o ide)-salt systems. For example, the mine line, and available only as an aqueous solu-

Spolymer (PEI) dissolves many of the sae al- tin. Linear poly(ethylene imine) was pre-

. kali metal salts as the ether polymer as evi- pared following the procedure of Saegusa et" danced by a loss in crystallinity of the ale,10 which involves hydrolysis of poly-

*polymer, the absence of x-ray diffraction from (N-acetyl ethylene imine) which in turn was

the added salt, and an increase in the glass' polymerized by the methyl iodide-initiatedtransition temperature. In the case of sodiu ring-opening polymerization of 2-methyl

iodide in PEI, a new crystal phase is formed oxazoline in dimethyl formmitde solution.

. which malts near 1SO 'C rather then near NS *C Lithit salts of F, cr", or, I., Scir,which is the malting point of the unadulter- C104" W 4 and CFSO3" were dehydrated by

ated polymer. The molar ratio of Na/N in the heating in a vacuum. Dried liner PEI and ancomplex is about 1/3 rather than the 1/4 ratio apprpriato mount of anhydrous salt to yield

"-.' " * ')' .v"- . "--" ", " ' ' " .'',", ".""." ," "." ."","".""," ." ." ." ," ." " "."z .., "

.W

a mlar ratio of salt to monomer of 0.1 were lar ratio of Li/(-CHCNH-) of 1/10 are showndissolved in spectra grade acetonitrile at in Figure 1 for PEI-LiCF3S03. Trace (a) wasreflux temperature (ca. 82 *C). The resulting obtained when heated at 20 C/ale for theuniform solution was then evaporated to dry- first time. It shows an indication of a glassness by evacuating for several days at 100 *C. transition at -13 C and an endothermic peakS . Differential Scanning Calorimetry at 52.8 C attributed to the melting of PEI

DSC scans were measured using a crystals. Upon cooling from the molten statePerkin-Elmer OSC-II equipped with a data sta- at 20 C/mtn, one obtains trace (b) whichtin11 . Smples were hermetically sealed in shows only the glass transition with no evi-an argon-filled dry box and heating and cool- dence of a crystallization exotherm. [The

II ing rates were usually 20 C/mia. HIting same polymer without the addition of salt ex-tmperatures reported herein refer to the peak hibits a sharp exotherm upon cooling.] Subse-temperature of the endothermal peak at the quent heating and cooling cycles, traces (c)normal scanning rate and glass transition tem- and (d), show only a change in heat capacity;pratures are reported as the aid point of the no first order transitions. If stored at roomchange in heat capacity. teprature for several days, crystallizationC. Conductivity Measurements does occur and the characteristics of trace

To avoid measurement problems associated (a) can be reproduced.with polarization at the electrodes, C can- The sam SC characteristics were obseredductivity was deduced from Cole-Cole plots ofAC impedance data obtained over the frequencyrange from 100 Nz to 13 az12 . AC impedancewas determined using a computerizedHewlett-Packard model 3470 network analyzer 11 .The sample cell consisted of two thin stain-less steel electrodes and a glass saple cup.When loading the smple into the conductivity acell, it was exposed to atmospheric conditionsI:; for about 10 minutes and was subsequentlydried by evacuating overnight followed by b

heating to the highest measuring temperature(usually 140) with continued evacuation foranother 20 to 40 hours. Impedance data werefirst obtained upon cooling from the highesttemperature in steps of five to ton degrees, dallowing 30 minutes for thermal equilibrimat each temperature. Impedance data were

also obtained during subsequent heating and -40 0 40 so 120cooling cycles."- 11M[RATUMfE (*C)

3. RESULTSTypical OSC traces of Pit containing a e- FI GUR of P-LiCF3SO3 comlexe.

ON T c of -* -of'" n '

.. J..

for all of the lithium salts listed above ex- Data obtained from the same sample upon heat-

cept LiF. In this case, there was essentially ing exhibit an abrupt change between 4S and

no change in the melting point of the PEI 50 OC which is the region in which uncamplexed

crystals. crystallization of the polymer was polymer undergoes a phase change. Recall that

observed upon cooling, and evidence for a crystallization is not observed upon cooling

glass transition in the temperature range ex- this system at 20 OC/min in the DSC but the

mined was absent. The only indication we cooling rates used for the conductivity mes-

have so far that LiF has dissolved in the urments are necessarily much slower and some

polymer is that the degree of crystallinity crystallization my be occurring. The active-

has been reduced. tion energy for tonic conduction seem to de-

The OC conductivity results for PEI con- pend upon the presence or absence of polymer

taining 0.1 mole of LiCIO4 per mole of maoner crystals - much as in the case of

repeat are shown as a function of reciprocal poly(ethylene oxide) - salt systms 3. below

temperature in Figure 2 for both cooling and 45 OC, the apparent activation energy is 1.35

heating cycles. Conductivity data obtained eV but decreases to 0.72 eV for temperatures

during the cooling cycle exhibit a smooth but above 80 OC. Both the values of conductivity

curved variation with reciprocal temperature. and activation energies are similar to those

10

Ida

10 0

FIG= 2o o •

- •

tio •f i m•meau.( aig i fiVs e"e .( aiga 11"O 0.olig

10 4 10.

B •

o4 • 4o

SFIGURE 2 FKIUE 3COdutivity of PIK *LtCl0a cinplez as a fimc- Condutivity of PUI-LiU, conples as a fune-

" tion Of inverse tenpertu~e. (e heating; tiom of inverse tuiperetire. (a heating;oc• ooling) o coolilng)

reported for comparable levels of L'C104 In greatest effect on crystallinity which is con-pEO13.sistent with the idea that salts of low lat-

DC conductivity as a function of recipro- tics energy are most readily dissolved2.*cal temperature is shown in Figuret 3 for PEI According to the lattice energies compiled by

containing 0.1 =ule of LiBF4 We mole of mono- Shriver et 1112, 11SF4 has the lowest lattice* inr repeat. -Hysteresis in conductivity upon energy of the salts examined here but its of-*heating and cooling in the region of melting fect on crystallinity (as cast from

and crystallization of the polymer is much acetonitrile) is not as great as most of the*more pronounced in this system. Apparent ac- other salts. When cooled at 20/mln from

tivatlon energies above and below the crystal- above the melting point of the polymer how-lization region are 0.56 eV and 1.64 eV, ever, all the salts except LiF prevented crys-

-respectively. tallizatlon of the polymer.

The glass transition tomeature of poly-4. DISCUSSION ethylene imine) was not observed directly in

The poly~ethylen imine) prepared by t our measurements. It is probably below -40 *Cprocedure described is of rather low molecular which is the lower range of our present OSC

*weight. about 2,000. and crystallizes readily equipenit. The presenice of 801 crystallinity*into a brittle material. Broad line Mi pro also makes it difficult to determine. How-

ton resoance spectra can be resolved Into a over, in other work. we have cross-linked the*narrow line comonent which we attribute to PCI with varying levels of diepoxyoctane which*protons in the Nmorpheus region and a broad prevents crystallization and introduces a

component attributable to protons within the clearly observed Tg within the range of our*crystalline phase. A samle whose degree of OSC. Extrapolation of these data to zero con-

crystallinity was 801 as determined by MM ex- centration of cross-links yields -35 OC as anhibits a heat of fusion (by KCS) of 55.3 cal/g estimate of Tg which is listed in Table 1.

*(231.5 J/g). From these data we deduce, that Again, all of the salts except LIF cause anthe heat of fusion of the crystalline phase is

* 69.1 cal/g (28.3 Jig) which we use in subse-Iquent estimates for deg.e of crystallinity in Table I

PEI to which lithium salts have been added. Complex formation of PEI and Lithium Salto*As mentioned previously. a reduction in degree C fl %~MI N* of crystallinity Implies that the added salt

*interacts strongly with the polymer ad at Litm CaneaNg. bliq (utbuiw POMm GIMleast some of it must be dissolved. Heats of 1 * Ne -

4.fusion were obtained on the first heating cy- LW . MY~ U.U 30.7* - d following removal of the acetonitrile; ex- LiC I#~ NR 4.3 -4I ~~capt for the case of LIP, there is no L ~ . ~ I

endothermic peag If reheated imediately. Thet Llp I IL MCI 0.8 -13

OSC reults wre summarized in Table I wher -e m ,, n, -the observed enthalpies are expressed in U11 I L A 66 _1

grm of Polymer (i.e. corrected for salt a WIL U. 4content). Thle CF3 03 _ (triflate) salt has the LW 0 US 33 US -

Ll*,*, 5 ILI 6.al 1.1 -13

increase of Tg. Presumbly, LI* ions act as crystallites through which the ions cannotcross-links by Interacting with unshared elec- move will require that the ions migrate

tron pairs on the nitrogens of neighboring through a more tortuous path which will reducechains. An increase in Tg is further evidence conductivity but one would not expect this to

for the dissolution of salt by the polymer14, greatly influence the apparent activation en-

All of the lithiu salts exained (except orgy for conduction. Since the ions are dis-

LiF) have about the sam effect on the glass solved in the amorphous regions of this

transition temperature as obtained from OSC polymer, the removal of part of this phase by

scans at 20*mtin. Conductivity data shown in crystallization will Increase the oncentra-

Figures 3 and 4 for LiC10 4 and LtUF 4 represent tion of ions in the remaining amrphous phase

the highest and loest Tg's of the very lim- which in turn can cause an Increase in Tg and

i Ited range. The system containing L1F 4 ex- reduce mobility of ions in the polymer. Fur-

hibits a larger conductivity than that of thermore, if the motion of ions boved to a

LIC1O4 over the wole range of temperature polymer chain depends upon the segmental mo-

which is consistent with greater mobility in bility of the polymer chain, such motion can

the system of lower Tg. The conductivities be expected to be greatly Inhibited by Incor-

are in the sam range as those reported for poration of a part of the chain in a polymer

poly(othylene oxide) - salt systMs13,15. as- crystal.

pecIally above the melting point of the PEI. Conductivity data obtained upon cooling

The pronounced hysterbsis in conductivity the PEI containing LCIO4 covers a large tem-

between heating and cooling in the PEI-LI1F 4 perature range over which the polymr remains

system of Figure 3 is associated with the almost completely amorphous. When plotted as

melting and crystallization of polymer cry- a function of reciprocal temperatre, the data

tals. Super cooling and slow crystallization are represented by a curved line reminiscent

are phenomena usually observed in polymers but of the tmperature dependence of viscosity

the dissolution of salt in the polymers which has been noted for other polymer-salt

, discussed here enhances these effects. When systms4 . Assuing that conductivity varies

* cooled from above the melt, the conductivity inversely with viscosity, the data can be fit

. decreases smoothly with decreasing temperature very well to a form of the WLF equgtion16,17:

until about SO "C where it suddenly decreases on -*exp[(-CIC2/(T-To)] (1)

over a narrow temperature range and then as- where r Is conductivity, T Is temperature, C1

sumes a smooth decrease again with a higher and C2 are constants related to fractional

" activation energy than at higher temperatures. free volie and Its variation with

The rapid decrease coincides with polymer temerature, * is the conductivity at

: crystallization. Upon reheating, the polymer times oC1 , and To is a temprature parameter.

crystals persist until about 700 and the con- To is related to the glass transition

ductivity is consequently lower between 50 and teperature through the relation:

700 than it was during cooling through this To e Tg - C2 (2)

sam region. The reasons for reduced conduc- Values of the parameters obtained fe, a least

tivity in the presence of polymer crystals squares fit to the data are To - 1U K and

have not been determined but one can speculate CICa 930 K. From the value of TV in Table

on possibilities. Certainly the presence of 1. we deduce that C * and C1 14.1 which

f*

- -* !.- ~ ~ ~ ;. .* .~. ** %*%~.~.. . .***

WTI- .T. 77 'P .P.'. ... M.A %sr.

are close to the "universal" values of 51.6 ACKNOWLEDGMJENT

and 17.4, respectively. The data can be fit Partial support of this work by the Office

equally as well to empirical equations of the of Naval Research is gratefully acknowledged.

form:( A/T) exp [-B/(T-To)] (3) REFERENCES

oro * -A/TI 1/2 ) exp [-/(T-T0 )] (4) 1. J. N. Parker and P. V. Wright, Polymer

where A. B, and TO are constants. 14 (1973) 589.

2. 0. F. Shriver, B. L. Papke, N. A. Ratner,5. CONCLUSIONS R. Oupon, T. Wong, and N. Brodwin, Solid

Linear poly(ethyleneimine) has been shown State Ionics 5 (1981) 83.

to dissolve the lithium salts of C1", Br-, 1-, 3. J. E. Weston and B. C. H. Steele, SolidState tonics 7 (1982) 81.SCN', CI04 , F4 , and CF3 SO3 " at concentra-

tions of I mole of salt to 10 moles of mnomer 4. N. B. Armand, J. M. Chabagno, and M. J.Duclot, Poly-ethers as solid

repeat. If LiF dissolves, it is to a lesser electrolytes, in: Fast Ion Transport inextent than the other salts. Dissolution is Solids, ads. P. Vashishta, J. N. Nundy.

and G. K. Shenoy (North-Holland,evidenced by a decrease in crystallinty of Amsterdam, 1979) pp. 131-136.the normally semicrystalline polymer, an in-

S. N. Watanabe, J. Ikeda, and 1. Shinohara,crease in the glass transition temperature and Polymer J. 15 (1983) 65.large increases in conductivity. No evidece 6. N. Watanabe, 3. Ikeda, and I. Shinohara,for a high-melting specific crystalline com- Polymer J. IS (1983) 175.

plex between the linear PEI and Li salts has7. R. Oupon, 1. L. Papke, N. A. Ratner, and

been observed. Temperature dependence of DC D. F. Shriver, J. Electrochm. Soc. 131conductivity as deduced from AC impedance (1984) 586.

analysis shows a change in slope at the melt- 8. C. K. Chiang, 6. T. Davis, C. A. Harding.ing point of the PEI crystals. Hysteresis be- and T. Takahashi, Nacromolecules 19

tween heating and cooling is observed in sm (195) 825.

cases in the region of crystallization and 9. T. Saegusa, H. Ikeda, and H. Fujit,Necrimolecules 5 (1972) 108.mlting showing greeter conductivity in an

undercooled saple than In a samicrystalline 10. T. Saegusa, H. Ikeda, and H. Fujii,Polymr J. 3 (1972) 35.samle at the sae temperature. For poly-

mer-salt systems in which crystallization is 11. Certain cmrcial equipment,instruments, or materials are identified

suppressed during the time scale of the elec- in this paper in order to adequatelyspecify the experimental procedure. Such

trical measurements, the conductivity data as identification does not imply

a function of temperature are wel1-represented recommendation or endorsement by theby an empirical equation similr to the WLF National Bureau of Standards nor does it

oimply that the material or equipment

equation which describes the temperature de- identified is necessarily the best

pendence of viscosity. The paremeters deduced available for the purpose.

from a least squares fit to the data yield 12. C. K. Chiang, J. R. Sethin, A. L. Dragoo,constants similar to those of the 14F @qua- A. 0. Franklin, and K. F. Young, J.Electrochm. Soc. 129 (1982) 2113.

tton,13. J. E. Weston and 3. C. H. Steele, Solid

State tonics 2 (1961) 347.

.1%

I(

I,

14. 0. 1. Jams, R. E. Wetton, and 0. S.Brow, Polymer 20 (1979) 187.

15. G. T. Oavis and C. K. Chiang, High IonicConduction in Polymers, in: HighConductivity Polymers, ad. H. Sasabe(Chemical Marketing Center, Tokyo. 1983)pp. 244-265.

K 16. J. 0. Ferry, Viscoelastic Properties ofPolymers (John Wiley & Sons, New York,1961).

17. M. L. Williams, R. F. Landel, and J. 0.Ferry, J. M. Chem. Soc. 77 (1955) 3701.

I,

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